2-substituted alkoxy-1, 4-diaminoanthra-quinone photographic dyestuffs



United States Patent 3,246,016 Z-SUBSTITUTED ALKOXY-l,4-DIAMINOANTHRA-QUINONE PHOTOGRAPHIC DYESTUFFS John F. Downey, Lexington, and Myron S.Simon,

Newton Center, Mass, assignors to Polaroid Corporation, Cambridge,Mass., a corporation of Delaware No Drawing. filed June 25, 1965, Ser.No. 467,108 5 Claims. (Cl. 260-377) This application is acontinuation-in-part of our copending application, Serial No. 152,014,filed November 13,, 1961.

This invention relates to photography and more particularly to novelchemical compounds particularly useful in photographic processes andproducts.

It is one object of the present invention to provide novel chemicalcompounds useful for the development of exposed silver halide emulsions.

Another object is to provide novel anthraquinone dyes which exhibit theproperties of a silver halide developing agent. These anthraquinone dyesmay therefore be referred to as dye developers or, more particularly, asanthraquinone dye developers.

Other objects of the invention will in part be obvious and will in partappear hereinafter.

The invention accordingly comprises the processes involving the severalsteps and the relation and order of one or more of such steps withrespect to each of the others, and the products and compositionspossessing the features, properties and the relation of elements whichare exemplified in the following detailed disclosure, and the scope ofthe application of which will be indicated in the claims.

The anthraquinone dye developers disclosed herein are particularlyuseful in the treatment of a latent image present in a photosensitiveelement, such as an exposed silver halide emulsion, whereby a positivedye image thereof may be imparted to another element, herein referred toas an image-carrying or image-receiving element.

US. Patent No. 2,983,606, issued May 9, 1961, to Howard G. Rogers,discloses difiusion transfer reversal processes wherein a photographicnegative material, such as a photographic element comprising an exposedsilver halide emulsion, is developed in the presence of a dye developerto impart to an image-receiving layer a reversed or positive dye imageof the developed image by permeating into said emulsion a suitableliquid processing composition and bringing said emulsion into superposedrelationship with an appropriate image-receiving layer. The inventiveconcepts herein set forth provide novel dye developers for use in suchprocesses.

In carrying out such processes, a photosensitive element containing asilver halide emulsion is exposed and wetted with a liquid processingcomposition, for example, by immersing, coating, spraying, flowing,etc., in the dark, and the photosensitive element superposed, prior to,during or after wetting, on an image-receiving element. In a preferredembodiment, the photosensitive element contains a layer of dyedeveloper, and the liquid processing composition is applied to thephotosensitive element in a uniform layer as the photosensitive elementis brought into superposed position with an image-receiving element. Theliquid processing composition permeates the emulsion to provide asolution of dye developer substantially uniformly distributed therein.As the exposed silver halide emulsion is developed, the oxidationproduct of the dye developer is immobilized or precipitated in situ withthe developed silver, thereby providing an imagewise distribution ofunoxidized dye developer dissolved in the liquid processing composition.This immobilization is apparently due, at least in part, to a change inthe solubility characteristictics of the dye developer upon oxidation,and especially as regards its solubility in alkaline solutions. It mayalso be due, in part, to a tanning effect on the emulsion by theoxidized developing agent. At least part of this imagewise distributionof unoxidized dye developer is transferred, by imbibition, to asuperposed image-receiving layer, said transfer substantially excludingsilver or oxidized dye developer. The imagereceiving layer receives adepthwise diffusion, from the emulsion, of unoxidized dye developer,without appreciably disturbing the imagewise distribution thereof, toprovide a reversed or positive, colored image of the developed ornegative image. The image-receiving element may contain agents adaptedto mordant or otherwise fix the diffused, unoxidized dye developer.Imbibition periods of approximately one minute have been found to givegood results, but this contact period may be adjusted where necessary tocompensate for variations in temperature or other conditions. Thedesired positive image is revealed by separating the image-receivinglayer from the photosensitive element at the end of the imbibitionperiod.

The dye developers of this invention may be utilized in thephotosensitive element, for example in, on or behind the silver halideemulsion, or they may be utilized in the image-receiving element or inthe liquid processing composition. In a preferred embodiment, a coatingor layer of the dye developer is placed behind the silver halideemulsion, i.e., on the side of the emulsion adapted to be located mostdistant from the photographed subject when the emulsion is exposed andpreferably also adapted to be most distant from the image-receivinglayer when in superposed relationship therewith. Placing the dyedeveloper behind the emulsion layer, as in the preferred embodiment, hasthe advantage of providing increased contrast in the positive image andalso minimizes any light-filtering action by the colored dye developer.In this preferred embodiment, the layer of dye developer may be appliedby using a coating solution containing, e.g., about 0.5 to 8%, byweight, of the dye developer. Similar concentrations may be used if thedye developer is utilized as a component or" the liquid processingcomposition. In an especially useful mode of disposing the dyedevelopers in the photosensitive elements, the dye developer isdissolved in a water-immiscible solvent and then dispersed in a gelatincoating solution.

The liquid processing composition which is used in the processes hereindisclosed comprises at least an aqueous solution of an alkalinecompound, for example, diethylamine, sodium hydroxide or sodiumcarbonate, and may contain the dye developer. In some instances, it maycontain an additional silver halide developing agent. If the liquidprocessing composition is to be applied to the emulsion by being spreadthereon, preferably in a relatively thin, uniform layer, it may alsoinclude a viscosityincreasing compound constituting film-formingmaterial of the type which, when spread over a water-absorbent base,will form a relatively firm and relatively stable film. A preferredfilm-forming material is a high molecular weight polymer such as apolymeric, water-soluble ether inert to an alkali solution, as, forexample, a hydroxyethyl cellulose or sodium carboxymethyl cellulose.Other filmforming materials or thickening agents whose ability toincrease viscosity is substantially unaffected when left in solution fora long period of time may also be used.

The novel dye developers of this invention are anthraquinone dyes havingthe formula (1) H IIIHz oR -NHi:i-R -z i NH:

wherein R is an alkylene or alkylene-oxyalkylene group, R is an alkylenegroup and Z is an orthoor paradihydroxyphenyl radical.

As examples of alkylene radicals comprehended by R and R mention may bemade of radicals such as z-- z 2,- z)3 2)4 2-)5,

It is intended that R may include an alkylene group and an intralinearcyclic component, e.g.,

In a preferred embodiment, R is an alkylene group contain'mg between 2and 10 carbons, and more preferably 3 to 7 carbons. R is preferably analkylene group comprising 1 to 4 carbons and more preferably a methyleneor ethylene group. It should be understood that R may be an alkylenegroup comprising 10 or more carbons, and R may be an alkylene groupcomprising 4 or more carbons, providing that the resulting dye developeris capable of being dissolved in the liquid processing compositiondescribed herein and its oxidation product rendered immobile. Z ispreferably a para-dihydroxyphenyl radical.

It should be understood that, when desired, the anthraquinone nucleusmay be substituted by one or more other substituents such as amino,alkyl, aryl, halogen, alkylamino, aryloxy, alkoxy, hydroxyl,sulfonamido, alkylsulfonamido, arylsulfonamido, carboxamido, carboxyl orsulfo radicals. It will be understood that when the anthraquinonenucleus is substituted with a carboxyl, sulfo, or other solubilizinggroup, care should be taken in selecting other substituents andprocessing conditions so that the oxidized dye developer will be lessmobile in the processing composition than the unoxidized dye developer.

The dye developer within Formula 1 may be prepared by condensing ananthraquinone of the formula:

CHr-C H:

( (I? IfHa A R NHa i O NHz wherein R has the same meaning as above, witha compound of the formula:

wherein R has the same meaning as above and Z is the protectedderivative, preferably, the acyl derivative and, more preferably, thebis-acetoxy derivative of the orthoand para-dihydroxyphenyl radical, andremoving the protective groups, as by hydrolysis. This method ofpreparation is particularly useful in preparing compounds within Formula1 wherein R comprises more than 2 carbons.

When R is one or two carbons, the compounds Within Formula 1 may beconveniently prepared by reacting one mole of a compound within Formula2 with one mole of a compound of the formula:

(4) O O l wherein n is an integer from 1 to 2.

In addition to the homogentisic acid lactones within Formula 4, the dyedevelopers of this invent-ion may also be prepared by reacting gentisicacid lactones and the substituted derivatives thereof with a compoundwithin Formula 2.

Compounds Within Formula 2 may be prepared by reacting 1,4 diamino 2phenoxyanthraquinone with the amino-alcohol according to the methoddisclosed in US. Patent No. 1,943,876, issued January 16, 1934, whereinan alcohol is reacted with 1,4-diamino-Z-phenoxyanthraquinone.

As examples of amino-alcohols that are useful in this preparation toprovide compounds wherein R is alkylene or alkoxy, mention may be madeof:

HO-C Hz-QCHPNHZ In particular, the dye developers of thisinvention-provide highly useful magenta dye developers which have beenfound to possess outstanding light stability characteristics in afinished photographic print, and-are substantially more light stablethan may azo and other anthraquinone magenta dye developers. Whenutilized in the diffusion transfer process, the dye developers of thisinvention are found to-possess good transfer characteristcs and givehigh density images.

As examples of useful compounds which may be used, e.g., in the form ofan acyl chloride within Formula 3 or as a lactone within Formula 4,mention may be made of:

CH2COOH I OH homogentisic acid CHPC'HPC O OH p-dihydroxyhydroclnnamlcacid I @wm-on-ooon I I OH a-methyl-2,5-dihydroxyhydrocinnamic acida-ethy1-2,5-dihydroxy-hydrocinnamtc acid HO I CHs-OOOH HO3,4-dlhydroxyphenylacetlc acid 110- ICHa-CH2COOH HO3,4-d1hydroxyhydr0cinnamic acid Although Z has been described as anorthoor paradihydroxyphenyl radical, it'should be understood that incertain instances one may desire to use other silver halide developingradicals to provide the silver halide developing function in the dyedeveloper, for example, a dihydroxy-substituted naphthalene radical. Itshould also be understood that the radical Z may contain substituentsother than those which supply the silver halide developing ability; suchsubstituents include alkyl, alkoxy, h-ydroxy, halogen, etc. groups.

Where a compound of formula 3 is used in the synthesis, it may bedesirable to protect the hydroxyl groups, which supply the developingfunction possessed by Z, by acylation, for example, to avoid sidereactions or oxidation. The protective groups are removed, as bybydrolysis, prior to photographic use.

As examples of dye developers within the scope of this invention,mention may be made of:

II I

II N112 I) NH:

1,4-d1amin0-2- ['y-(2,5'-dihydroxy) -hydroclnnainido]-amoxy-anthraquinone (III) 1,4-diamin0-2 ['y- (2',5-dihydroxy)-hydrocinnamido] -propoxyanthraquinone 1,4-diamino-2-[B-(2',5-dihydroxy) -hydrocinnamtdo-fiethyl] -ethoxy-anthraquinone (XIV)l mit 0 OH A oonnrNm i-c in-om OH;

H O N H: O H

The following nonlimiting examples illustrate the preparation of dyedevelopers within the scope of this invention.

Example I A liter flask was charged with 34.9 grams of1,4-diamino-2-(e-arnino)-amoxy-anthraquinone, 29.4 grams of2,5-di-hydroxy-hydrocinnamic acid lactone and 350 cc. of alcohol. Theflask was fitted with a condenser and Bunsen valve, deaerated withnitrogen and the contents heated 16 hours on the steam bath. The mixturewas then cooled to 25 C., and a deaerated solution of 13.5 grams ofsodium hydroxide was added to the flask. The flask was then filled withdeaera-ted water and allowed to stand 30 minutes. Carbon dioxide wasbubbled in until no further change of pH occurred. The mixture was thenfiltered and washed with 3% hydrochloric acid until the filtrate wascolorless. The solid was then washed with water until acid-free. Thesolid was recrystallized from isopropyl alcohol. The resulting1,4-diamino-2-[' -(2,5- dihydroxy)-hydrocinnamido] -arnoxy anthraquinonemelted at 157-158 C. and had a spectral absorption curve with A at 577;e=16,000.

Example II 1,4-diamino-2-(p homogentisamido) ethoxy anthraquinone wasprepared according to the procedure of Example I using1,4-diamino-2(f3-amino)-ethoxy anthra- Example 111 1,4-diamino-2-['y-(2',5' dihydroxy)-hydrocinnamido]- propoxy anthraquinone wasprepared according to the procedure of Example I using1,4-dia1nino2-(a-amino)- propoxy anthraquinone and2,5-dihydroxyhydrocinnarnic acid lactone. The product melted at 141-144C.

Example IV 1,4-diamino-2-[fl-(2',5'-dihydroxy) hydrocinnamidofl-ethyl]-ethoxy anthraquinone was prepared according to the procedure of ExampleI using 1,4-diarnino-2-(flamino)-fl-ethyl-ethoxy anthraquinone and2,5-dihydroxyhydrocinnamic acid lactone. The product melted at 124134 C.

The following examples of the photographic utilization of the dyedevelopers of this invention are given for purposes of illustrationonly.

Example V A photosensitive element was prepared by coating a gelatinsubcoated film base with a solution comprising 0.38 g. vof1,4-diamino-2-[' -(2,5'-dihydroxy)-hydrocinnamido]-amoxy-anthraquinonedissolved in cc. of a solution of 2% cellulose acetate hydrogenphthalate in acetone. After this coating dried, a blue-sensitive silveriodobromide emulsion was applied and allowed to dry. This photosensitiveelement was exposed, and brought into superposed relationship with animage-receiving element as an aqueous liquid composition comprising:

Water, cc. 100 NaOH, g. 5.17 Hydroxyethyl cellulose (high viscosity)[commercially available from Hercules Powder Co., Wilmington 99,Delaware, under the trade name Natrosol 250], g. 4.03 Sodiumthiosulf-ate, g. 1.15 Benzotriazole, g. 2.3 N-benzyl-a-picoliniumbromide, g. 2.3

8 was spread between said elements. The image-receiving elementcomprised a 2:1 mixture, by weight, of polyvinyl alcohol andpoly-4-vinylpyridine on a baryta paper support. After an imbibitionperiod of approximately one minute, the image-receiving element wasseparated and contained a magenta positive image.

7 Example VI The procedure described in Example V was repeated, exceptthat the dye developer was dispersed in a layer of gelatin. The coatingsolution from which the dye developer layer was coated was prepared byadding 0.57 g. of the dye developer dissolved in 1.5 cc. ofN-n-butylacetanilide and 2 cc. of cyclohexanone to 5 g. of 10% gelatinsolution, 1.3 cc. of Water at 40 C., and 1 cc. of 5% Alkanol B.Emulsification was effected by high speed agitation in a Waring Blendor.5 cc. of the resulting dye dispersion was added to 10 cc. of watercontaining small amounts of saponin and succinaldehyde, and

then coated on the gelatin subcoated cellulose acetate film base. I

Substitution of the other dye developers described above in theprocedures described in Examples V and VI gave similar positive transferimages.

It has been found that if the dye developers of this invention containsome of the anthraquinone triamine intermediate dyes, desensitization ofthe silver halide emulsion may occur if the emulsion is in contact witha layer containing the dye developer. Accordingly, precautions should betaken to remove unreacted anthraquinone triamine prior to photographicuse. Also, known procedures for handling dyes which exhibit a tendencyto desensitize may be used. 7

The dye developers of this invention are also useful in integralmultilayer photosensitive elements for use in multicolor diffusiontransfer processes. As an example of such photosensitive elements,mention may be made of the photosensitive elements disclosed and claimedin the copending US. application of Edwin H. Land and Howard G. Rogers,Serial No. 565,135, filed February 13, 1956, wherein at least twoselectively sensitized photosensitive strata are superposed on a singlesupport and are processed, simultaneously and without separation, with asingle common image-receiving element. .A suitable arrangement of thistype comprises a support carrying a red-sensitive silver halide emulsionstratum, a green-sensitive silver halide emulsion stratum and ablue-sensitive silver halide emulsion stratum, said emulsions havingassociated therewith, respectively, a cyan dye developer, a magenta dyedeveloper and a yellow dye developer. In one of the preferredembodiments of photosensitive elements of this type, the dye developersare disposed in separate alkali-permeable layers behind thephotosensitive silver halide emulsion stratum with which they areassociated.

The photosensitive elements within the scope of this invention may beused in roll film units which contain a plurality of photosensitiveframes. The photosensitive elements of this invention are especiallyuseful in composite roll film intended for use in a Polaroid LandCamera, sold by Polaroid Corporation, Cambridge 39, Massachusetts, or asimilar camera structure such, for example, as the camera forming thesubject matter of US. Patent No. 2,435,717, issued to Edwin H. Land onFebruary 10, 1948. In general, such composite roll films comprise aphotosensitive roll, a roll of image-receiving material and a pluralityof pods containing an aqueous alkaline processing solution. The rollsand pods are so associated with each other that, upon processing, thephotosensitive element may be superposed on the imagereceiving elementand the pods may be ruptured to spread the aqueous alkaline processingsolution between the superposed elements. The nature and construction ofthe pods used in such units are well known to the art. See,

9 for example, U.S. Patents Nos. 2,543,181 and 2,634,886, issued toEdwin H. Land.

It will be noted that the liquid processing com-position may contain oneor more auxiliary or accelerating silver halide developing agents, suchas p-methylaminophenol (Metol); 2,4-diaminophenol (Amidol);benzylaminophenyl; hydroquinone; a substituted hydroquinone such astoluhydroquinone, phenyl-hydroquinone, or 4-methylphenylhydroquinone; ora 3-pyrazolidone such as 1- phenyl-3-pyrazolidone. These auxiliarysilver halide developing agents are substantially colorless, at least intheir unoxidized form. It is possible that some of the dye developeroxidized in exposed areas may be oxidized by an energy transfer reactionwith oxidized auxiliary silver halide developing agent.

In addition, development may be effected in the presence of an oniumcompound, particularly a quaternary ammonium compound, in accordancewith the processes disclosed and claimed in the copending application ofMilton Green and Howard G. Rogers, Serial No. 50,851, filed August 22,1960 (now U.S. Patent No. 3,173,786, issued March 16, 1965).

The dye developers of this invention may be used also in conventionalphotographic processes, such as tray or tank development of conventionalphotosensitive films, plates or papers to obtain black and white,monochromatic or toned prints or negatives. By way of example, adeveloper composition suitable for such use may comprise an aqueoussolution of approximately 12% of the dye developer, 1% sodium hydroxide,2% sodium sulfite and 0.05% potassium bromide. After development iscompleted, any unreacted dye developer is Washed out of thephotosensitive element, preferably with an alkaline washing medium orother medium in which the unreacted dye developer is soluble. Theexpression toned is used to designate photographic images wherein thesilver is retained with the precipitated dye, whereas monochromatic isintended to designate dye images free of silver.

It should be noted that the dye developers of this medium areself-suflicient to provide the desired color image and do not dependupon coupling reactions to produce the desired color. They thus providea complete departure from conventional photographic color processes inwhich the color is produced by a coupling reaction between a colorformer or coupler and the oxidized developing agent, as Well asso-called auto-coupling processes in which color is obtained by areaction of the oxidized developing agent with unoxidized developingagent.

It will be apparent that, by appropriate selection of theimage-receiving element from among suitalble known opaque andtransparent materials, it is possible to obtain either a coloredpositive reflection print or a colored positive transparency. Likewise,the inventive concepts herein set forth are adaptable for multicolorwork by the use of special photographic materials, for example, filmmaterials of the type containing two or more photosensitized elementsassociated with an appropriate number of imagereceiving elements andadapted to be treated with one or more liquid processing compositions,appropriate dye developers suitable to impart the desired subtractive 10colors being incorporated in the photosensitized elements or in theliquid processing compositions. Examples of such photographic materialsare disclosed in U.S. Patent No. 2,647,049, issued to Edwin H. Land onJuly 28, 1953.

As examples of useful image-receiving materials, mention may be made ofnylon, e.g., N-methoxymethylpolyhexamethylene adipamide, polyvinylalcohol, and gelatin, particularly polyvinyl alcohol or gelatincontaining a dye mordant such as poly-4-vinylpyridine.

The image-receiving element also may contain a development restrainer,e.g., 1-phenyl-5-mercaptotetrazole, as disclosed in the copendingapplication of Howard G. Rogers and Harriet W. Lutes, Serial No. 50,849,filed August 22, 1960.

The inventive concepts herein set forth are also adaptable for theformation of colored images in accordance with the photographic productsand processes described and claimed in U.S. Patent No. 2,968,554, issuedto Edwin H. Land on January 17, 1961.

The novel compounds herein disclosed are also suitable for use as dyesfor textile fibres, such as nylon.

In the preceding portions of the specification the expression color hasbeen frequently used. This expression is intended to include the use of.a plurality of colors to obtain black.

Since certain changes may be made in the above products, compositionsand processes without departing from the scope of the invention hereininvolved, it is intended that all matter contained in the abovedescription shall be interpreted as illustrative and not in a limitingsense.

What is claimed is:

1. An anthraquinone dye of the formula:

wherein R is selected from the group consisting of alkylene andalkylene-oxyalkylene, each said alkylene containing no more than fivecarbon atoms, R is an alkylene group containing no more than four carbonatoms, and Z is a para-dihydroyphenyl radical.

2. 1,4-diamino-2-(B-homogentisamido)-ethoxy anthraqumone.

3. 1,4 diamino-Z-['y-(2',5'-dihydroxy)-hydrocinnamido]-amoxyanthraquinone.

4. 1,4 diamino-2-['y-(2,5'-dihydroxy)-hydrocinnamido] -propoxyanthraquinone.

5. 1,4 diamino-2-[/3-(2',5'-dihydroxy)-hydrocinnamido-B-ethyH-ethoxyanthraquinone.

No references cited.

LORRAINE A. WEINBERGER, Primary Examiner.

R. K. JACKSON, Examiner.

H. C. WEGNER, Assistant Examiner.

1. AN ANTHRAQUINONE DYE OF THE FORMULA: